Low sulfur tall oil fatty acid

ABSTRACT

The invention relates to tall oil fatty acid compositions having low sulfur content, as well as methods of using and making the same.

The present invention is related to, and claims the benefit of 119(e)priority to U.S. provisional patent application Ser. No. 60/708,425;entitled “Low Sulfur Tall Oil Fatty Acid”, which was filed on Aug. 15,2005, and is hereby incorporated, in its entirety, herein by reference.

FIELD OF THE INVENTION

The invention relates to tall oil fatty acid compositions having lowsulfur content, as well as methods of using and making the same.

BACKGROUND OF THE INVENTION

Economic and environmental considerations are forcing great marketdemand for renewable resources of raw materials, such as those utilizedin the transportation industry. Examples include the fuel and fuelpackage market. As standards increasingly require sulfur content withinfuels to be reduced, fuel packages and fuel additives must also coincidewith such regulations. Therefore, there is a great need for fuels, fuelpackages, and fuel additives to have low sulfur content therein.

Tall oil products such as tall oil fatty acid (TOFA), derivativesthereof such as esters and alcohols, as well as fatty acid compositionscontaining the same is one such source of such fuels and/or fueladditives. TOFA and/or its derivatives, for example, are considered veryvaluable as a fuel and/or fuel additive due to their low temperaturestability properties, especially as compared to vegetable and/ornon-woody-based oil and/or fatty acid products. However, sulfur speciesare introduced into tall oil products during the Kraft process, whichincludes the addition of sodium sulfide and sodium hydroxide to woodchips for digestion, and then the neutralization/acidification of thebasic mixture with sulfuric acid. Both of these processes can generatesulfur species, organic and/or inorganic alike, which are carried alongwith the black liquor soap, and then into the crude tall oil (CTO).Further refinement through fractional distillation of the CTO generallyconcentrates the sulfur species into specific product streams (pitch,rosin, and heads); however it does not eliminate the sulfur species fromTOFA.

Until now, tall oil fatty acid was seen in the art as having anundesirable level of sulfur content therein to be efficiently utilizedin, or as, environmentally-friendly fuels, fuel packages, and fueladditives, especially since the inception of new laws restrictingenvironmentally unfriendly emissions from the automobile industry. Thedrive for more environmentally friendly automobiles which contain moderntechnologies will require low sulfur fuel, fuel additives and fuelpackages. Otherwise, the presence of such traditional levels of sulfurmay “poison” such technology, substantially reducing the lifespan ofthis technology; and thus, being economically inefficient.

In addition, high sulfur content in tall oil products, such as TOFA,prohibits the downstream conversion of such products into usefulvalue-added chemistries. One example of such a conversion is thehydrogenation of tall oil products into alcohols. Another example is thehydrogenation of dimer acids as well as Monomer (CAS Registry Number68955-98-6) Conventional tall oil products contain so much sulfur thathydrogenation catalysts are contaminated by the these sulfur containingspecies, thus “killing” or “poisoning” the catalyst and making theconversion of such conventional tall oil products very economicallyinefficient and undesirable. Thus, there exists a need to create talloil products from renewable resources in a manner so as to ensure lowsulfur content therein and maintain low temperature stability thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: shows the results when distilled or undistilled TOFA issubjected to various amounts (1-5%) silica adsorbent to make oneembodiment of the composition according to the present invention.

FIG. 2 shows the results when distilled or undistilled TOFA is subjectedto various amounts (1-5%) clay adsorbent.

DETAILED DESCRIPTION OF THE INVENTION

This application is related to the fields of chemistry and chemicalengineering which is described, for example, in Kirk-Othmer“Encyclopedia of Chemical Technology”, fourth edition (1996), John Wiley& Sons, which is hereby incorporated, in its entirety, herein byreference.

The inventors have surprisingly found a composition that is relativelylow cost and environmental friendly for use as or in a fuel, fuelpackage, and/or fuel additive. This composition is a renewable resourceand is especially suitable for use in the diesel or gasoline markets.The composition comprises biomass and/or byproducts thereof. Thus, thecomposition is a renewable resource. Examples of a biomass product maybe the byproducts of paper making from trees such as tall oil products.Accordingly, biomass products, such as those similar to black liquorsolids, soaps, skimmings, as well as tall oil products such as pitchand/or distillate products thereof are examples of such biomassproducts. Further, such biomass products of the present invention arepredominantly environment friendly, especially compared to thosetraditional tall oil products. Finally, the composition of the presentinvention has low sulfur content and preferably exhibits low temperaturestability.

The present invention provides a method for reducing the sulfur contentof a fatty acid-containing composition (FAC), and also provides fattyacid-containing compositions that demonstrate low sulfur content.Further, the present invention relates to methods of making and usingsuch fatty acid-containing compositions.

As used herein, the terms “fatty acid” and “fatty acids”, whether inreference to linear, branched or cyclic fatty acids, are usedinterchangeably, and both terms refer to one or more compounds of theformula R¹—COOH wherein R¹ is a hydrocarbon having at least 4 carbonatoms that is optionally substituted with one or more hydroxyl groups,or derivatives thereof. Further, the —COOH group is an acid group. Thefatty acid may contain any number of hydroxyl groups and may vary widelybased upon the number of carbon atoms present in the fatty acid. Forexample, the fatty acid may contain at least 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,28, 29, and 30 hydroxyl groups. As used herein, the term hydrocarbonrefers to a chemical group formed entirely of carbon and hydrogen. Theterm “optionally substituted with one or more hydroxyl groups” refers tothe replacement of a hydrogen atom of the hydrocarbon with a hydroxyl(—OH) group. The R¹ group typically has no more than 99 carbons, so thatthe fatty acid has a total of no more than 100 carbons. In variousembodiments of the invention, the R¹ group has at least 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,28, 29, or 30 carbons. The present invention provides embodimentswherein the maximum number of carbons in the R¹ group is, in variousembodiments, 99, 90, 80, 70, 60, 50, 40, 39, 38, 37, 36, 35, 34, 33, 32,31, or 30 carbons. In a preferred embodiment, R¹ contains 4-29 carbons,more preferably 7-25 carbons, and most preferably from 15 to 23 carbonatoms.

The fatty acids may contain, n, acid functional groups, where n may befrom 1 to 10, preferably from 1 to 6 acid functional groups, morepreferably from 1 to 3 acid functional groups.

The “fatty acid” or “fatty acids” of the present invention may be asingle fatty acid structure or may be a mixture of different fatty acidstructures. Regardless of the purity or composition, for convenience indescribing the present invention, the fatty acid that is being modifiedto provide reduced sulfur content will be referred to herein as thefatty acid-containing composition, or FAC for short. For instance, theFAC may be pure stearic acid, oleic acid, and/or linoleic acid, whereinR¹ is C₁₇. As used herein “C_(n)” refers to a group having “n” number ofcarbons. In the case of stearic acid, R¹ has 17 carbons. As used herein,“pure” refers to a concentration of fatty acids of 99-100 weight percentof the referenced fatty acids based on the total weight of fatty acidsin the mixture/composition/blend.

As referred to herein, the FAC that is modified to provide low sulfurcontent is, in various embodiments of the present invention, inadmixture with no more than 99 wt % of non-fatty acid material, or, invarious other embodiments of the invention, no more than 99, 98, 97, 96,95, 90, 80%, or 70%, or 60%, or 50%, or 40%, or 30%, or 20%, or 10%, or5%, or 3%, or 1%, or less than 1% such as 0.1 wt %, 0.01 wt %, 0.001 wt%, or 0.0001 wt % of non-fatty acid material, where these weight percentvalues are based on the entire weight of the composition.

As another example, the FAC may be a mixture of fatty acids. That is, acomposition containing two or more fatty acids having non-identical R¹groups. For instance, the FAC may contain branched and/or cyclic fattyacids. In a preferred embodiment, the FAC contains a majority, i.e.,greater than 50%, of fatty acids, on a weight percent basis, based onthe total weight of fatty acids in the composition. In anotherembodiment, the FAC contains a minority, i.e., less than 50%, of fattyacids, on a weight percent basis, based on the total weight of fattyacids in the composition

In one exemplary embodiment of the present invention, the FAC containspredominantly C₁₂₋₂₄ fatty acids (R¹═C₁₁₋₂₃), while in anotherembodiment the FAC contains predominantly C₁₆₋₂₀ fatty acids(R¹═C₁₅₋₁₉). In other exemplary embodiments of the present invention,the FAC contains at least 90% C₁₂₋₂₄ fatty acids (R¹═C₁₁₋₂₃), while inanother embodiment the FAC contains at least 90% C₁₆₋₂₀ fatty acids(R¹═C₁₅₋₁₉).

Independent of the number of carbons in the hydrocarbon, in variousembodiments of the present invention the R¹ group may be, branched, orcyclic, and independently may be saturated or unsaturated. The termunsaturated includes both monounsaturated and polyunsaturated, wherepolyunsaturated includes 2, 3, 4 or more sites of unsaturation. A siteof unsaturation is a double bond between two adjacent carbons of R¹.

In one aspect of the invention, the R¹ groups in the FAC are primarilyunsaturated, i.e., at least 50 mol % of the fatty acids in the FAC has aR1 group that is unsaturated. In various embodiments of the presentinvention, at least 50%, 60%, 70%, 80%, 90% or 95% of the R¹ groups inthe FAC are unsaturated. In one aspect, the fatty acids are primarilysaturated, i.e., at least 50 mol % of the fatty acids does not have adouble bond in the R¹ group. Thus, in various embodiments of the presentinvention, and for each of the above-recited percentage amounts of R¹groups in the FAC, at least 50%, 60%, 70%, 80%, 90%, 95% or 98% of theR¹ groups are saturated, with the remainder of the R¹ groups beingunsaturated.

In another aspect of the invention, the R¹ groups in the FAC areprimarily cyclic and/or polycyclic, i.e., at least 50 mol % of the fattyacids in the FAC has a cyclic R¹ group. Thus, in various embodiments ofthe present invention, at least 50%, 60%, 70%, 80%, 90% or 95% of the R¹groups are cyclic. In one aspect, the cyclic fatty acids are primarilysaturated, i.e., at least 50 mol % of the cyclic fatty acids does nothave a double bond in the R¹ group. Thus, in various embodiments of thepresent invention, and for each of the above-recited percentage amountsof cyclic R¹ groups in the fatty acids, at least 50%, 60%, 70%, 80%,90%, 95% or 98% of the R¹ groups are unsaturated, with the remainder ofthe R¹ groups being saturated.

In another aspect of the invention, the R¹ groups in the FAC areprimarily linear, i.e., at least 50 wt % of the fatty acids in the FAChas a cyclic R¹ group. Thus, in various embodiments of the presentinvention, at least 50 wt %, 60%, 70%, 80%, 90% 95%, 97, 98, 99, 99.9,99.99, or 99.999 of the R¹ groups are linear. In this aspect, the amountfatty acids having linear R¹ groups may be from 50 to 99.999 wt %,preferably from 85 to 99.999 wt %, based upon the total weight of theFAC. The amount of fatty acids having linear R¹ groups may be 50, 55,60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, and 99.999wt % based upon the total weight of the FAC, including any and allranges and subranges therein.

In addition, the amount of fatty acids having cyclic R¹ groups may befrom 0.001 to 50 wt %, preferably from 0.1 to 15 wt %, based upon thetotal weight of the FAC. Thus, in various embodiments of the presentinvention, not more than 50 wt %, 40%, 30%, 20%, 15% 10%, 9, 8, 7, 6, 5,4, 3, 2, 1, 0.1, 0.01, and 0.001 wt % of fatty acids having R¹ groupsthat are cyclic are present in the FAC. The amount of fatty acids havingcyclic R¹ groups may be 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2,1, 0.1, 0.01, and 0.001 wt % based upon the total weight of the FAC,including any and all ranges and subranges therein.

In one aspect of the invention, the R¹ group is a hydroxyl-substitutedhydrocarbon. In one aspect, the hydrocarbon is substituted with a singlehydroxyl group. Suitable FAC having hydroxyl-substituted hydrocarbon R¹groups include fatty acids derived from castor oil, e.g., ricinoleicacid and hydroxystearic acids.

According to the present invention, the fatty acid may be a branchedchain fatty acid (BCFA). In one aspect of the invention, the BCFA is asaturated BCFA that may be described by the following formula, whereineach of x, y, and z is independently selected from 0-26:CH₃—(CH₂)_(x)—CH[(CH₂)_(y)CH₃]—(CH₂)_(z)—COOH wherein x+y+z=6-26. Invarious embodiments of the invention, x+y+z=6, or 7, or 8, or 9, or 10,or 11, or 12, or 13, or 14, or 15, or 16, or 17, or 18 as the lowerlimit on the number of carbon atoms represented by the sum of x, y andz. Independently, for each of these embodiments, the upper limit of thesum x, y and z is 26, or 25, or 24, or 23, or 22, or 21, or 20, or 19.In various embodiments of the invention, y+z=6, or 7, or 8, or 9, or 10,or 11, or 12, or 13, or 14, or 15, or 16, or 17, or 18 as the lowerlimit on the number of carbon atoms represented by the sum of y and z.Independently, for each of these embodiments, the upper limit of the sumy and z is 26, or 25, or 24, or 23, or 22, or 21, or 20, or 19. Invarious embodiments of the invention, x+y=6, or 7, or 8, or 9, or 10, or11, or 12, or 13, or 14, or 15, or 16, or 17, or 18 as the lower limiton the number of carbon atoms represented by the sum of x and y.Independently, for each of these embodiments, the upper limit of the sumx and y is 26, or 25, or 24, or 23, or 22, or 21, or 20, or 19.

While the above example is that of a saturated BCFA, the BCFA may beeither saturated or unsaturated as discussed above generally with regardto the FAC.

Examples which come within this group and are offered commercial are:2-methylpropanoic (isobutyric)—(Hoechst, Eastman); 2-methylbutanoic(isopentanoic)—(Union Carbide); 3-methylbutanoic (isovaleric)—(Hoechst);2,2-dimethylpropanoic (neopentanoic)—(Exxon); isooctanoic—(Hoechst);2-ethylhexanoic—(Eastman, Union Carbide); and 2,2-dimethyloctanoic(neodecanoic)—(Exxon).

The BCFA of the present invention contains at least one branch point onthe carbon chain of the fatty acid. However, the BCFA may contain morethan one branch point and still be a BCFA according to the presentinvention. For instance, a BCFA may have two or more methylsubstituents, or two or more ethyl substituents, or one methyl and oneethyl substituent, etc. In one aspect of the invention, the BCFA is amono-unsaturated branched chain fatty acid. In another aspect of theinvention, the BCFA is a poly-unsaturated branched chain fatty acid.

Cyclic fatty acids (CFA) include, without limitation, rosin and/or resinacids, where such acids include, for example, abietic acid, levopimaricacid, neoabietic acid, palustric acid, dehydroabietic acid, isopimaricacid, sandaracopimaric acid, pimaric acid, communic acid, andsecodehydroabietic acid. Other sources of cyclic fatty acids includeTall Oil, Tall Oil Heads, Distilled Tall Oil, Pitch, and Rosin, whereeach of these materials is a product of the distillation of navalstores. See, e.g., Naval Stores—Production, Chemistry and Utilization,D. F. Zinkel and J. Russel (eds.), Pulp. Chem. Assoc. Inc., 1989.Further examples of CFA and derivatives thereof include those derivedfrom or sourced from wood rosin and/or gum rosin, including, but notlimited to, esters thereof, for example. In one embodiment of thepresent invention, the CFA are and/or are derived from resin and/orrosin acids. Examples of rosin acids may include those mentioned in U.S.Pat. Nos. 6,875,842; 6,846,941; 6,344,573; 6,414,111; 4,519,952; and6,623,554, which are hereby incorporated, in their entirety, herein byreference.

CFA also includes the internal cyclization product of fatty acid. Whenunsaturated fatty acid is heated, particularly in the presence of claycatalysts as occurs during formation of polymerized fatty acid, theunsaturated fatty acid may undergo an internal cyclization reaction andthereby form a cyclic fatty acid. Such cyclic fatty acids are CFA'saccording to the present invention. See, e.g., Naval Stores—Production,Chemistry and Utilization, D. F. Zinkel and J. Russel (eds.), Pulp.Chem. Assoc. Inc., 1989.

BCFA and CFA can be obtained from many sources. For instance, suppliersof fine and bulk chemicals may sell BCFA and CFA. See, e.g., AcrosOrganics (Pittsburgh Pa.), Aldrich Chemical (Milwaukee Wis., includingSigma Chemical and Fluka), Apin Chemicals Ltd. (Milton Park UK), AvocadoResearch (Lancashire U.K.), BDH Inc. (Toronto, Canada), Bionet(Cornwall, U.K.), Chemservice Inc. (West Chester Pa.), Crescent ChemicalCo. (Hauppauge N.Y.), Eastman Organic Chemicals, Eastman Kodak Company(Rochester N.Y.), Fisher Scientific Co. (Pittsburgh Pa.), FisonsChemicals (Leicestershire UK), Frontier Scientific (Logan Utah), ICNBiomedicals, Inc. (Costa Mesa Calif.), Key Organics (Cornwall U.K.),Lancaster Synthesis (Windham N.H.), Maybridge Chemical Co. Ltd.(Cornwall U.K.), Parish Chemical Co. (Orem Utah), Pfaltz & Bauer, Inc.(Waterbury Conn.), Polyorganix (Houston Tex.), Pierce Chemical Co.(Rockford Ill.), Riedel de Haen AG (Hannover, Germany), Spectrum QualityProduct, Inc. (New Brunswick, N.J.), TCI America (Portland Oreg.), TransWorld Chemicals, Inc. (Rockville Md.), and Wako Chemicals USA, Inc.(Richmond Va.), to name a few.

The above-listed chemical suppliers may also sell the correspondingalcohols, i.e., compounds of the formula R¹—CH₂—OH, which can beoxidized to the desired BCFA or CFA by techniques well known in the art(see, e.g., Fuhrhop, J. and Penzlin G. “Organic Synthesis: Concepts,Methods, Starting Materials”, Second, Revised and Enlarged Edition(1994) John Wiley & Sons ISBN: 3-527-29074-5; Hoffman, R. V. “OrganicChemistry, An Intermediate Text” (1996) Oxford University Press, ISBN0-19-509618-5; Larock, R. C. “Comprehensive Organic Transformations: AGuide to Functional Group Preparations” 2nd Edition (1999) Wiley-VCH,ISBN: 0-471-19031-4; March, J. “Advanced Organic Chemistry: Reactions,Mechanisms, and Structure” 4th Edition (1992) John Wiley & Sons, ISBN:0-471-60180-2; Patai, S. “Patai's 1992 Guide to the Chemistry ofFunctional Groups” (1992) Interscience ISBN: 0-471-93022-9; Solomons, T.W. G. “Organic Chemistry” 7th Edition (2000) John Wiley & Sons, ISBN:0-471-19095-0; Stowell, J. C., “Intermediate Organic Chemistry” 2ndEdition (1993) Wiley-Interscience, ISBN: 0-471-57456-2; “IndustrialOrganic Chemicals: Starting Materials and Intermediates: An Ullmann'sEncyclopedia” (1999) John Wiley & Sons, ISBN: 3-527-29645-X, in 8volumes; “Organic Reactions” (1942-2000) John Wiley & Sons, in over 55volumes; and “Chemistry of Functional Groups” John Wiley & Sons, in 73volumes.)

A preferred BCFA and CFA is a by-product of dimer acid production. Thedimerization of fatty acids, and particularly TOFA, to produce dimeracid, is well known in the art. See, e.g., Naval Stores—Production,Chemistry and Utilization, D. F. Zinkel and J. Russel (eds.), Pulp.Chem. Assoc. Inc., 1989. At the end of the dimerization process, duringpurification of the dimer acid, a mono-carboxylic acid distillationproduct is typically obtained, where this distillation product iscommonly referred to in the art as monomer acid or simply as “monomer”.Monomer is typically a mixture of branched, aromatic, cyclic, andstraight chain fatty acids, which may be saturated or unsaturated. Thepredominant acid in monomer is iso-oleic acid, a mixture of branched andcyclic C₁₈ mono-unsaturated fatty acids. The iso-oleic acid may berefined from monomer by low temperature solvent separation, in order toprepare a purified iso-oleic acid. Both monomer and the purifiediso-oleic acid is a BCFA of the present invention, where iso-oleic acidof about 90% purity is a preferred BCFA of the invention. Noteworthy isthat, as this example illustrates, BCFA need not be a pure material, butmay be in admixture with other materials, even fatty acids that are notbranched.

Either of monomer or the purified iso-oleic acid may be subjected to ahydrogenation process to provide the corresponding saturated BCFA, whereeither of these saturated BCFAs is a BCFA of the present invention.Hydrogenated iso-oleic acid is also known as iso-stearic acid.

Dimer acid is produced by many companies that generally produce productsbased on naval stores. Arizona Chemical (Jacksonville, Fla. USA;www.arizonachemical.com); Cognis Corp USA (division of Cognis BV;Cincinnati, Ohio USA; www.cognis.com); Hercules (Wilmington, Del. USA;www.herc.com), now Eastman Chemical; and Westvaco Corporation, ChemicalDivision (Charleston Heights, S.C. USA; http://www.westvaco.com) arefour examples. These companies, and others, also sell Monomer and/orrefined iso-oleic acid and/or the hydrogenation products thereof. Forexample, Arizona Chemical sells their CENTURY® fatty acids, whichtypically include BCFA. Whether a particular fatty acid contains BCFA orCFA can be readily determined by someone with skill in the art bysubjecting a sample of the fatty acid to gas chromatography and/or massspectrometry, and comparing the resulting chromatogram or mass spectrumto the chromatogram or spectrum of the corresponding pure, i.e.,reference material.

Other methods of producing BCFA and CFA may be found in, e.g., “FattyAcids in Industry” Chapters 7 and 11, edited by R. W. Johnson and E.Fritz, M. Dekker, New York, 1989, ISBN 0824776720.

In one aspect, the BCFA is or includesCH₃—CH[(CH₂)_(y)CH₃]—(CH₂)_(n)—COOH wherein y+z=6-26 and y=0, i.e., theBCFA is an “iso-acid”. In one aspect, the iso-acid contains a total of6-30 carbons. Iso-oleic and iso-stearic are two preferred iso-acid BCFAsof the present invention. The preferred branching in a BCFA is either amethyl or an ethyl branch.

The FAC may contain some linear fatty acid (non-BCFA and non-CFA), BCFAand/or CFA. If the FAC does contain some BCFA and/or CFA in addition tolinear fatty acid that is/are not branched (non-BCFA) or cyclic(non-CFA), then the ratio of non-BCFA:BCFA in the FAC is preferably isat least 60:40 or 70:30 or 80:20 or 90:10 or 95:05 or 98:02 or 99:01 orthe BCFA is less than 1 weight percent of the fatty acid in the FAC, andnon-CFA:CFA in the FAC is preferably 80:20 or 90:10 or 95:05 or 98:02 or99:01 or the CFA is less than 1 weight percent of the fatty acid in theFAC

In an additional embodiment, the FAC may contain a major portion ofBCFA. For example, in some cases, distillation products of tall oilcompositions and/or derivatives thereof may contain high amounts of BCFAas a major portion of the FAC. In some such cases the non-BCFA:BCFA inthe FAC may be at most 60:40 or 50:50 or 40:60 or 30:70 or 20:80 or10:90 or more than 99 weight percent BCFA of the fatty acid in the FAC.Examples of such compositions may be Monomer and isostearic acid. Anexample of Monomer is that which has been assigned CAS Registry Number68955-98-6, which is an alternative and distinct product from TOFA.Discussions of the differences between TOFA and Monomer can be found inUnited States Published Patent Application Numbers 20060009543;20050075254; 20040242835; 20040210029; 20040176559; and 20040024088,which are all hereby incorporated, in their entirety, herein byreference. One example of such a commercially available FAC having amajority of BCFA of the total fatty acid content is Century MO-6 sold byArizona Chemical Company. In a preferred aspect of this embodiment, theFAC contains CFA as well.

Derivatives of the fatty acid may be any commonly known derivative of acarbonyl-containing compound known in general Organic ChemistryTextbooks, such as “Organic Chemistry”, 5th Edition, by Leroy G. Wade,which is hereby incorporated, in its entirety, herein by reference.Examples of derivatives of the fatty acid may be an ester thereof ornitrogen-containing derivative thereof such as a nitrile, amide, oramine carboxylate (amide) thereof, as well as those commonly found inblack liquor solids, soaps, skimmings, as well as tall oil products suchas pitch and/or distillate products thereof.

One aspect of the present invention relates to ester containingderivatives of the fatty acid (fatty acid esters). Such derivatives maycontain at least one ester of the fatty acid such as those discussed inWO 2005/028597, which is hereby incorporated, in its entirety, herein byreference. The ester containing fatty acid may be of the formula:R¹—COOR², where R¹ is as discussed above and R² may be a substituted orunsubstituted hydrocarbon containing from 1 to 30 carbon atoms. R² maycontain 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms,including any and all ranges and subranges therein.

The —COOR² is an ester functional group. The fatty acid derivative maycontain, m, ester functional groups, where m may be from 1 to 10,preferably from 1 to 6 ester functional groups, more preferably from 1to 3 ester functional groups. Even further, the fatty acid derivativemay contain only n acid functional groups as discussed above, only mester functional groups, or a mixture of n acid functional groups asdiscussed above and m ester functional groups.

In one preferred embodiment, R² is a short chain alkyl group, includingbut not limited to a methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,iso-butyl, and tert-butyl group; the most preferred being methyl.According to such most preferred example of this embodiment, theresultant ester containing fatty acid would be a fatty acid methyl ester(FAME).

In another preferred embodiment, R² is a hydrocarbon substituted withone or more alcohol groups such as that described for R¹ above,including but not limited to polyols, glycols, etc. Examples include butare not limited to glycerol and ethylene glycol. According to such anexample of this embodiment, the resultant ester containing fatty acidwould be a fatty acid glyceryl ester. To create the above mentionedfatty acid esters, the fatty acid discussed above may be, for example,reacted with an R² precursor where the R² may be, but is not limited, toa hydrocarbon substituted with one or more alcohol groups. When thisoccurs in this non-limiting example, at least one fatty acid having theabove R¹—COOH formula may be reacted and covalently bound to an R²precursor where the R² may be, but is not limited, to a hydrocarbonsubstituted with one or more alcohol groups.

For example, a mono fatty acid ester may be produced if one fatty acidhaving the above R¹—COOH formula is reacted and covalently bound to anR² precursor where the R² may be, but is not limited, to a hydrocarbonsubstituted with one or more alcohol groups. Further, a difatty acidester may be produced if two fatty acids having the above R¹—COOHformula is reacted and covalently bound to one R² precursor where the R²may be, but is not limited, to a hydrocarbon substituted with two ormore alcohol groups. Still further, a trifatty acid ester may beproduced if three fatty acids having the above R¹—COOH formula isreacted and covalently bound to one R² precursor where the R² may be,but is not limited, to a hydrocarbon substituted with three or morealcohol groups. These examples are not meant to be limiting but toexemplify that the number of fatty acids that can covalently react viaan ester linkage with the R² precursor can be any number of fatty acidsup until all of the alcohol groups of the R² precursor is depleted.

In an additional non-limiting example, a fatty acid may be reacted withglycerol which has three alcohol groups (i.e. the R² precursor).According to the above exemplified embodiment the fatty acid may bereacted with glycerol in a manner to create a fatty acid derivativewherein the fatty acid derivative (only by a non-limiting example), maybe a monofatty acid glycerol ester, a difatty acid glycerol ester, and atrifatty acid glycerol ester.

In a preferred aspect of the present invention, the FAC is adistillation product from tall oil, and the FAC includes fatty acidscommonly associated with tall oil fatty acids (TOFA). In one aspect, theFAC contains TOFA. Further, the FAC may contain crude tall oil (CTO)and/or distilled tall oil (DTO). Examples of tall oil product sourcesare those commercially available from Arizona Chemical Company,including commercially available Sylfat products from Arizona ChemicalCompany, more specifically Sylfat 2, Sylfat 2LT, Sylfat FA1, Sylfat FA2,and Sylfat FA3. Still preferred fatty acid containing compositions maybe North American TOFA or distillates thereof, Scandanavian TOFA ordistillates thereof, including blends of each. Still further, each ofthese fatty acid containing compositions may be esterified as discussedabove, preferably methyl and/or glyceryl esters thereof.

Since BCFA contains at least one acid functionality similar to the fattyacids discussed above, derivations of the BCFA may exist such as thosedescribed for the fatty acid above. Therefore, in another aspect, theBCFA may be a derivative of BCFA, such as for example an ester- ornitrogen-containing derivative of BCFA when present in the FAC. Examplesof FAC's containing derivatives of BCFA are, without limitation, MonomerEsters. Examples of such would be esters of Century MO-6. Someexemplified esters may be Monomer glycerol esters, Monomer methylesters, and Monomer trimethylolpropane (TMP)-esters which arecommercially available for example from Arizona Chemical Company asUniflex product lines such as Uniflex 1803, Uniflex 336, and Uniflex936.

Thus, in one exemplary embodiment of the present invention, the FACcontains from 10-80% mono-saturated fatty acids, 10-80% poly-unsaturatedfatty acids, 0-50% saturated fatty acids, and 0-50% cyclic fatty acids.In another exemplary embodiment of the present invention, the FACcontains 40-60% mono-saturated fatty acids, 40-60% poly-unsaturatedfatty acids, less than 5% saturated fatty acids, and less than 10%cyclic fatty acids. In yet another exemplary embodiment of the presentinvention, the FAC contains 25-35% mono-unsaturated fatty acids, 55-80%poly-unsaturated fatty acids, less than 5% saturated fatty acids, andless than 10% cyclic fatty acids. In these embodiments, a preferredcyclic fatty acid is one, or a mixture of, resin acids.

Fatty acids may be saturated or unsaturated and the FACs of the presentinvention may contain one or the other or mixtures of both saturated andunsaturated fatty acids.

Saturated fatty acids include, without limitation, valeric acid, caproicacid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauricacid, myristic acid, palmitic acid, margaric acid, stearic acid,arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanicacid, and melissic acid.

Fatty acids may be mono- or poly-unsaturated fatty acids and the FACs ofthe present invention may contain one or the other or mixtures of bothmono- and poly-unsaturated fatty acids.

For example, unsaturated fatty acids include, without limitation,caproleic acid, palmitoleic acid, oleic acid, vaccenic acid, elaidicacid, brassidic acid, erucic acid, and nervonic acid.

For example, polyunsaturated fatty acids include, without limitation,linoleic acid, pinoleic, linolenic acid, eleostearic acid, andarachidonic acid.

In an embodiment, the FAC contains at least 50 wt %, preferably, atleast 60 wt %, more preferably at least 70 wt %, most preferably atleast 75 wt % of oleic and/or linoleic acid or derivatives thereof,based upon the total weight of the FAC. The FAC may contain from 50 to100 wt %, preferably from 60 to 99, more preferably from 65 to 95 wt %of oleic and/or linoleic acid or derivatives thereof based upon thetotal weight of the FAC. The FAC may contain 50, 55, 60, 65, 70, 75, 77,80, 82 85, 87, 90, 92, 95, 98 and 100 wt % of oleic and/or linoleic acidor derivatives thereof based upon the total weight of the FAC, includingany and all ranges and subranges therein.

In an additional embodiment, when the FAC contains both oleic andlinoleic acids or and/or derivatives thereof, the FAC may contain anyamount of oleic and linoleic acids or and/or derivatives thereof. It ispreferable that the weight ratio of oleic acid and/or derivative thereofto linoleic acid or derivative thereof is from 5:1 to 1:5, preferablyfrom 4:1 to 1:2, more preferably from 3.5:1 to 1:1, based upon the totalweight of the oleic acid and/or derivative thereof and the linoleic acidor derivative thereof. The ratio may be 5:1, 4:1, 3.9, 3.7:1, 3.5:1,3.2:1, 3.0:1, 2.7:1, 2.5:1, 2.2:1, 2.0:1, 1.8:1, 1.5:1, 1.2:1, 1:1,1:1.5; 1:2; 1:2.5; 1.3; 1:3.5; 1:4, 1:4.5, and 1:5, including any andall ranges and subranges therein.

Suitable FAC are available from many commercial suppliers, e.g., Uniqema(division of ICI; New Castle, Del. USA; www.uniqema.com); Cognis CorpUSA (division of Cognis BV; Cincinnati, Ohio USA; www.cognis.com); AkzoNobel Inc. (Chicago, Ill. USA; www.akzonobelusa.com); CrodaInternational Plc (East Yorkshire, U.K.; www.croda.com); ArizonaChemical (Jacksonville, Fla. USA; www.arizonachemical.com); GeorgiaPacific (Atlanta, Ga. USA; www.gp.com); Hercules (Wilmington, Del. USA;www.herc.com) now Eastman Chemical; and Westvaco Corporation, ChemicalDivision (Charleston Heights, S.C. USA; http://www.westvaco.com).

Addition examples of fatty acids and derivatives thereof, as well as theexemplified FACs, are described in WO1994017160; WO2006002683; andWO2005123890, which are hereby incorporated, in their entirety, hereinby reference.

Additional FAC's are those already having considerable low temperaturestability, including those described in WO 2004/013259, which is herebyincorporated, in its entirety, herein by reference. The low temperaturestability of the FAC may be determined by any of the following foursimple laboratory tests, which are exemplary only. These include, forexample, long-term storage, cloud point (CP), pour point (PP), and coldfilter plugging point (CFPP).

Low temperature stability may be determined by measuring the cloud pointof a sample. Determining the cloud point of a sample is a well-knowntechnique, and is described in ASTM D2500/IP219/ISO3015 from AmericanSociety for Testing and Materials (West Conshohocken, Pa.;http://www.astm.org). Many vendors sell equipment specifically designedto measure cloud point according to this ASTM procedure. See, e.g.,Herzog HCP 852 Pour & Cloud Point Analyzer from Walter Herzog GmbH(Lauda-Königshofen, Germany; a subsidiary of PAC Petroleum AnalyzerCompany L.P., Pasadena, Tex., USA; www.paclp.com); and CPP97-2A Version2 Automatic Cloud and Pour Point Analyzer from GT Instruments (adivision of Gecil Process; Saint-Cyr-au-Mont-d'Or, France;www.gecil.com). Essentially, the cloud point test cools a sample whilemonitoring for crystal formation. The cloud point is that temperature atwhich crystals begin to appear. A lower cloud point denotes better lowtemperature stability.

Low temperature stability may also be determined by monitoring theappearance of a cooled sample over an extended period of time. Thus, asample is placed in a container, and the container is placed into acooled environment. On a periodic basis, for example, daily, weekly, orbiweekly, the samples are visually examined for clarity. Clarity may bejudged on a scale of 1-10, where 1 is crystal clear and 10 is opaque.While this method does not provide unambiguous quantitative data, themethod is quite satisfactory for monitoring the relative low temperaturestability of several samples.

Differential scanning calorimetry (DSC) is another technique that may beused to determine low temperature stability. A sample may be subjectedto the following heating and cooling regime: heat from 25° C. to 100° C.@ 50° C./min; then hold at 100° C. for 2 min; then cool from 100° C. to−50° C. @ 10° C./min; then hold at −50° C. for 2 min; then heat from−50° C. to 100C @ 20° C./min. The DSC device is used to measureexotherms and endotherms that occur during this heating and coolingregime. A sample that demonstrates a relatively lower temperature ofcrystallization will have better low temperature stability according tothe present invention.

Other methods that may be used to measure the low temperature stabilityof a FAC or a mixture of FAC and LTS include, without limitation, thepour point of the material, where a lower pour point is indicative ofbetter low temperature stability. The pour point generally indicates thelowest temperature at which the composition can be pumped. Pour pointmay be measured by, e.g., ASTM D2500/IP219/ISO3015). Another suitabletechnique is the Low Temperature Flow Test (LTFT). See, e.g., ASTM D4539and Canadian General Standards Board CAN/CGSB-3.0-No. 140.1.

The FAC may also be, for example, a fuel or biofuel, such as thosedescribed below. Accordingly, the fuel or biofuel may act as the FAC,for example, in one aspect as defined herein.

Although the FAC may contain any amount of sulfur, preferably the FACcontains low amounts of sulfur. Preferably, the FAC contains less than50 ppm sulfur based upon the total weight of the composition. Thecompositions may be low sulfur and/or ultra low sulfur compositions suchas compositions containing at most 25 ppm, at most 15 ppm, at most 10ppm, and/or at most 5 ppm sulfur based upon the total weight of thecompositions. The sulfur content includes any volatile and/ornon-volatile sulfur containing species and/or compounds, including thosethat are either organic and/or inorganic sulfur containing compounds.The composition may contain not more than 50, 45, 40, 35, 30, 25, 22,20, 18, 15, 12, 10, 8, 6, 5, 4, 3, 2, 1, 0.1, 0.01, 0.001, 0.0001, and0.00001 ppm of sulfur, including any and all ranges and subrangestherein. In some aspects of the invention, the composition may be sulfurfree or essentially sulfur free by containing no and/or trace amounts ofsulfur.

The amount of sulfur present in the FAC may be determined by anyconventional manner of measuring sulfur content therein. Preferably, thesulfur content may be measured by standard tests, including ASTM D 5453(using an Antec device) with UV fluorescence and/or ASTM D1822 withX-ray fluorescence.

In one embodiment, the FAC may contain at least one unsaponifiablematerial. Examples of unsaponifiable materials is found, but not limitedto, those described in U.S. Pat. Nos. 6,875,842; 6,846,941; 6,344,573;6,414,111; 4,519,952; 6,623,554; 6,465,665; 6,462,210; and 6,297,353which are hereby incorporated, in their entirety, herein by reference.Unsaponifiable material may be any neutral material that is not capableof being saponified, or ester thereof. Examples of unsaponifiablematerials is found, but not limited to, those described in U.S. Pat.Nos. 6,875,842; 6,846,941; 6,344,573; 6,414,111; 4,519,952; and6,623,5546,465,665; 6,462,210; and 6,297,353, as well as United StatesPatent Application Publication Numbers 20060052462 and 20060041027 whichare hereby incorporated, in their entirety, herein by reference. Furtherexamples include, without being limited, stilbenes and fatty alcoholesters.

The composition may have an acid value. Preferably acid values includethose greater than 10, including greater than or equal to 10, 11, 12,13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90,95, 100, 105, 110, 120, 125, 130, 140, 150, 160, 170, 180, 190, and 200,including any and all ranges and subranges therebetween. Preferably, theacid value of the composition is greater than or equal to 120, mostpreferably greater than or equal to 180.

Preferably, the composition of the present invention is a fuel and/orfuel additive composition and/or package composition containing from 0.1to 99.999 wt %, more preferably from 85 to 99.999 wt % of at least onesaturated or unsaturated, monocarboxylic aliphatic hydrocarbon orderivative thereof having a linear, branched, and/or cyclic chain offrom 8 and 24 carbon atoms, a dimer thereof, a trimer thereof, ormixtures thereof based upon the total weight of the composition; from0.001 to 99.9 wt %, preferably from 0.001 to 15 wt % of at least onecyclic fatty acid, preferably rosin acid compound, selected from thegroup consisting of natural resin-based acids obtained from residues ofdistillation of natural oils, amine carboxylates and ester and nitrilecompounds of these acids based upon the total weight of the composition;and not more than 25 ppm, preferably not more than 15 ppm, of sulfurbased upon the total weight of the composition. All ranges and subrangeswithin those amounts disclosed above may be utilized.

The present invention may be used in lieu of, or in addition to, one ormore other methods that can be employed to address the problem ofunsatisfactory performance of fatty acids for intended end uses such asin the fuel industry. For example, methods of improving the lowtemperature stability of fatty acids and/or to further reduce theamount/concentration of sulfur in the FAC may be used. While the lowtemperature stability of the FAC is very good, the fuel industry isconcerned about the low temperature stability of fatty acids in general;and, may most often turn to one exemplified solution that is focused onthe use of heated FAC storage tanks, and/or the addition of solvent,typically hydrocarbon solvent, to the FAC, in order to address theperceived problem of low temperature stability. The use of addition ofsolvent also may serve to further dilute or lower the concentration ofthe sulfur in the FAC. Thus, according to the present invention, a FACmay be placed into a heatable storage tank and heated to a sufficienttemperature that the low temperature outside the storage tank, i.e., theambient temperature, does not detrimentally affect the stability of theFAC within the tank.

The FAC may be required to be stable and/or perform at low temperatures.Low temperature stabilizers (LTSs) may be added to the FAC to furtherimprove the FAC's performance at low temperatures. The LTS may be anycomponent that may be added to a FAC so as to improve its lowtemperature stability, including freezing and/or cloud pointsuppressants. Examples of LTS's include, without limitation, glycols.Examples of glycols may be but is not limited to polyethylene glycols(PEG), as well as propylene and/or ethylene glycol. Further examplesinclude, without limitation alcohols such as for example lower alkylalcohols such as for example isopropyl alcohol. Still further, the LTSsmay those mentioned in U.S. patent application Ser. No. 11/393,387,filed Mar. 29, 2006, having publication number ______, entitled“COMPOSITIONS CONTAINING FATTY ACIDS AND/OR DERIVATIVES THEREOF AND ALOW TEMPERATURE STABILIZER”, which is hereby incorporated, in itsentirety, herein by reference. Still further, examples of the LTSinclude polyamides. Examples of polyamides include without limitationEster-Terminated PolyAmides (ETPAs), Tertiary-Amide-TerminatedPolyAmides (ATPAs), Ester-Terminated PolyEster-Amides (ETPEAs), TertiaryAmide-Terminated PolyEster-Amides (ATPEA), PolyAlkyleneOxy-terminatedPolyAmides (PAOPAs), and PolyEther-PolyAmides (PEPAs). These polyamides,as well as their respective methods of making the same, are described inU.S. Pat. Nos. 5,783,657; 6,268,466; 6,552,160; 6,399,713; and6,956,099, which is hereby incorporated, in its entirety, herein byreference.

When the FAC contains the optional polyamide as an LTS, the FAC containsfrom 10 ppm to 80 wt % polyamide based on the total weight of theFAC:polyamide composition, including all ranges and subranges therein,may be added to the FAC. This may include at least 10, 20, 30, 40, 50,60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 175, 200, 225, 250, 300,350, 400, 450, 500, 550, 600, 650, 700, 750, 1000, 2000, 3000, 4000,5000, 6000, 7000, 8000, 9000, and 10000 ppm polyamide, including any andall ranges and subranges therein. Further, this may include at most 80,75, 70, 65, 60, 65, 60, 55, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40,35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01,0.005, and 0.001 wt % polyamide, including any and all ranges andsubranges therein.

Preferred polyamides are those polyamides commercially available fromArizona Chemical Company, most preferably Sylvaclear A2612, Sylvagel5600, Sylvagel 5000, Sylvagel 6000, Sylvagel 4000, Sylvaclear 100,Sylvaclear 100LM, Sylvaclear C75v, Uniclear 100, and Uniclear 100v.

The LTS and FAC may be contacted with each other via mixing, blending,etc. The contacting may occur while applying heat, after applying heat,or before applying heat.

Some solvent may be added to the FAC in order to either further enhancethe low temperature stability of the mixture or to achieve a dilution ofthe sulfur content of the FAC. Suitable solvents for this purpose arewell known and currently used in commercial settings. Some of thesesolvents are: aromatic hydrocarbons, non-aromatic cyclic hydrocarbons;hydrocarbons, branched hydrocarbons, saturated hydrocarbons. Specificsolvents known by their chemical names include xylene, heptane, andkerosene. Specific solvents known by their commercial names includeSHELLSOL™ heptane and CYCLO SOL™ 100 Aromatic solvent (both from ShellChemical Company, Houston, Tex. USA; www.shellchemicals.com); SOLVESSO™100 and 150, which are but two suitable “Aromatic Fluids” sold byExxonMobil Chemical (Houston, Tex., USA; www.exxonmobil.com/chemical);and Caromax™ products such as Caromax™ 20 sold by Petrochem Carless.Preferably, the solvent contains a majority of xylene or isomersthereof, most preferably 100 wt % xylene, when it is used according tothe present invention.

Still likewise, a cosolvent may be added to the FAC. Examples of thecosolvent include alcohol containing cosolvents, especially when the FACcontain esters of fatty acids and optionally contains an LTS that ispreferably a polyamide. The most preferred alcohol containing cosolventsare low molecular weight alcohols, including but not limited to thosealcohols having the following formula: R³OH, where R³ a hydrocarboncontaining from 1 to 20 carbon atoms. The hydrocarbon may contain 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20carbon atoms and may be linear or branched. Preferably, the cosolvent isethanol and/or 2-ethyl hexanol. The cosolvent may be used in addition toor in lieu of the solvent described above.

The optional LTS may be added to the optional solvent or optionalcosolvent prior to, after, and/or at the same time as it is contactedwith the FAC. Alternatively, the solvent and/or cosolvent may be usedalone or individually.

Again the use the LTS, heat, solvent, and/or cosolvent are eachindividually optionally used with or added to the FAC of the presentinvention. Any one or more of them, as well as other conventional meansfor improving the low temperature stability and/or removing (ordiluting) the sulfur concentration of the FAC may be used in connectionwith the FAC of the present invention as well as methods of making andusing the same.

The FAC according to the present invention may be used as a fueladditive and/or a fuel blend component, for instance, as a lubricityimprover and/or as a fatty acid alkyl ester containing fuel. In anembodiment of the present invention, when the FAC contains a fatty acidalkyl ester, such as for example a fatty acid methyl ester, the FAC maybe the fuel, preferably a biofuel. Suitable fuels which mayadvantageously be combined with the FAC of the invention include,without limitation, middle distillates, diesel, gas oil, gasoline,aviation fuel, biofuel and kerosene. The fuel may also be a low sulphurfuel and/or an ultra low sulfur fuel. The fuel may have a sulfurcontent, i.e., <500 ppm or <350 ppm or <50 ppm or <25 or <15 ppm or <10ppm, based upon the total weight of the composition. Further, the fuelmay also be sulfur free or essentially sulfur free containing no sulfurand/or trace amounts of sulfur.

The FAC may either be added directly to the fuel, or it may form part ofa fuel additive package, where such packages are common in the fueladditive industry. The FAC may include the above-mentioned LTS and/orsolvent and/or cosolvent prior to its addition to the fuel and/or fueladditive package. Other components that may be present in the fueladditive package are one or more of detergent, cold flow additive,antifoam, static dissipator, antioxidant, and others additives as usedin the art.

In a preferred embodiment, about 20 parts per million (ppm) to 100 wt %of the FAC in the fuel may be necessary, based upon the total weight ofthe composition. In fact, when the FAC may be used as a fuel itself, theFAC component may take up to 100 wt %, based upon the total weight ofthe composition. Therefore, in one embodiment, about 20 ppm to 20 wt %of the FAC in the fuel may be necessary, based upon the total weight ofthe composition. The amount of the FAC may vary and is dependent uponthe function of the FAC in the fuel. For example, about 20 to 1000 ppmof the FAC is preferable in instances where the FAC is utilized toafford improved lubricity to the fuel.

In various aspects, the present invention provides a method of improvingthe performance of a fuel by adding to that fuel a performance-enhancingamount of a FAC, where the mixture has better low temperature stabilityand/or lubricity than does the fuel alone. In another embodiment, thepresent invention provides a fuel having both FAC and LTS, where thecombination of FAC and LTS is present at a concentration of about 50 ppmto about 20 wt % based on the total weight of the composition. Inanother aspect, the present invention provides a fuel prepared by theprocess of combining fuel, FAC and LTS, where these three components arecombined in any order, and the FAC and LTS are, in total, present in thefuel at a concentration effective to enhance the performance of thefuel, preferably from 50 ppm to about 20 wt % based on the total weightof the composition.

Again, the LTS is optional and the FAC may be incorporated into the fuelat the above amounts without the LTS.

When the fuel and the FAC used as an additive are present in thecomposition, the FAC may be present at any amount sufficient to provideany level of desired lubricity to the fuel. In one embodiment where thefuel and FAC are present in a single composition, the FAC is present atan amount that is at least 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150ppm, 175 ppm, 200 ppm, 225 ppm, 250 ppm, 300 ppm, 400 ppm, and 500 ppm,and present at an amount that is equal to or less than 100, 90, 80, 70,60, 55, 50, 45, 40, 35, 30, 25, 20, 19, 18, 17, 16, 15, 10, 5, 4, 3, 2,1, 0.5, 0.1, 0.05, and 0.01 wt % based upon the total weight of thecomposition, depending upon whether the FAC is used as a fuel additiveor whether the FAC is the fuel or a major portion of the fuel. In eachof these fuels or methods to prepare a fuel when the LTS is present withthe FAC, the weight ratio of LTS to FAC in the fuel may be 1:1; 0.8:1;0.6:1; 0.4:1; 0.2:1 0.1:1; 0.09:1; 0.08:1; 0.07:1; 0.06:1; 0.05:1;0.04:1; 0.03:1; 0.02:1; 0.01:1; 0.008:1; 0.006:1; 0.004:1; 0.002:1;0.001:1; and 0.0001:1 of LTS:FAC.

In one embodiment of the present invention, the FAC composition is afuel itself, a lubricity improver, friction modifier, a fuel additivepackage, and/or mixtures thereof. For example, when at least a portionof the FAC is fatty acid alkyl ester, for example a fatty acid methylester, the resultant composition may be used directly as a fuel, forexample as a biofuel. In another example, when at least a portion of theFAC is for example a monoglycerol TOFA, the FAC may be used directly asa fuel additive. In an additional example, when at least a portion ofthe FAC is a TOFA-based triglyceride, the composition may be useddirectly as a fuel. Of course, other fuel additives such as an LTSand/or solvents and/or cosolvents may be a part of the above-mentionedcompositions.

The FAC of the present invention may be incorporated into additivepackages specifically tailored to the end use and/or function. When suchpackages are intended to be utilized in fuels, especially diesel fuels,such packages may include solvents, biocides, detergents, corrosiveinhibitors, cetane improvers, dyes, and antistatics. Preferably,packages are constructed with low sulfur-containing constituents,including, for example, those described in WO 2005/078052, which ishereby incorporated, in its entirety, herein by reference. Furtherexamples of fuels and additives known to be packaged and utilized insuch fuels are summarized and exemplified in the following Table.

TABLE 1 Representative fuels and additives known to be packaged andutilized in such fuels. Carrier Combustion Cetane Octane DetergentsDispersant Fluids Improver Improver Improver Ethers Major Blend SparkGasoline, Petrol, x x x x x x Components Ignition Petroleum EthersCompression Diesel, Gas Oils, x x x x x x Ignitio

Middle Distillates Aviation Jet Fuel, Kerosene x Fuel Heavy Heating Oil,Bunker x x x Fuel Fuel, Marine Fuel, Asphaltenes Synthetic Biomass toLiquid x x x x x x x Fuels BtL, Gas to Liquids GtL, Fischer TropschFuel, Minor Blend Oxygenates MTBE, ETBE, TAME, x x x Components TAEEBio-fuels Alcohols Ethanol, Methanol, x x x x x x Butanol, Alkyl c1-8Esters FAME, FAEE, x x x Triglycerides, Vegetable Oils Special GaseousLPG, CNG, DME, Fuels Hydrogen Wax Particulate Exhaust ColdFlow Anti-Smoke Filter After Improver Settling Vis- Icing Suppres- RegenerationTreatment CP/PP/ Additive cosity Inhib- sents Additives Additive CFPPWASA Modifer itors Major Blend Spark Gasoline, Petrol, x x ComponentsIgnition Petroleum Ethers Compression Diesel, Gas Oils, x x x x xIgnitio

Middle Distillates Aviation Jet Fuel, Kerosene x Fuel Heavy Heating Oil,Bunker x x x x x x Fuel Fuel, Marine Fuel, Asphaltenes Synthetic Biomassto Liquid x x x x x x Fuels BtL, Gas to Liquids GtL, Fischer TropschFuel, Minor Blend Oxygenates MTBE, ETBE, TAME, x Components TAEEBio-fuels Alcohols Ethanol, Methanol, x x Butanol, Alkyl c1-8 EstersFAME, FAEE, x x x x x x Triglycerides, Vegetable Oils Special GaseousLPG, CNG, DME, Fuels Hydrogen Corrosion Lubricity Friction De- Demul-Anti- Inhibitors Improver Modifiers haze sifier foam Major Blend SparkGasoline, Petrol, x x x x Components Ignition Petroleum EthersCompression Diesel, Gas Oils, x x x x x x Ignitio

Middle Distillates Aviation Jet Fuel, Kerosene x x x Fuel Heavy HeatingOil, Bunker x x x Fuel Fuel, Marine Fuel, Asphaltenes Synthetic Biomassto Liquid x x x x x x Fuels BtL, Gas to Liquids GtL, Fischer TropschFuel, Minor Blend Oxygenates MTBE, ETBE, TAME, x x x x Components TAEEBio-fuels Alcohols Ethanol, Methanol, x x x x x x Butanol, Alkyl c1-8Esters FAME, FAEE, x x x x x Triglycerides, Vegetable Oils SpecialGaseous LPG, CNG, DME, Fuels Hydrogen Static Metal Dissi- Deacti-Thermal Anti- Bio- pators vators Stabilizers oxidants cides Dyes MajorBlend Spark Gasoline, Petrol, x x x x x Components Ignition PetroleumEthers Compression Diesel, Gas Oils, x x x x x Ignitio

Middle Distillates Aviation Jet Fuel, Kerosene x x x x Fuel HeavyHeating Oil, Bunker x x x x Fuel Fuel, Marine Fuel, AsphaltenesSynthetic Biomass to Liquid x x x x x Fuels BtL, Gas to Liquids GtL,Fischer Tropsch Fuel, Minor Blend Oxygenates MTBE, ETBE, TAME,Components TAEE Bio-fuels Alcohols Ethanol, Methanol, x x x x x xButanol, Alkyl c1-8 Esters FAME, FAEE, x x x x x x Triglycerides,Vegetable Oils Special Gaseous LPG, CNG, DME, Fuels Hydrogen Lead Re-Compat- Surfac- Replacement Markers odourants ibilisers tants SolventAdditves Major Blend Spark Gasoline, Petrol, x x x x Components IgnitionPetroleum Ethers Compression Diesel, Gas Oils, x x x Ignitio

Middle Distillates Aviation Jet Fuel, Kerosene Fuel Heavy Heating Oil,Bunker x x x Fuel Fuel, Marine Fuel, Asphaltenes Synthetic Biomass toLiquid x x x x x Fuels BtL, Gas to Liquids GtL, Fischer Tropsch Fuel,Minor Blend Oxygenates MTBE, ETBE, TAME, x Components TAEE Bio-fuelsAlcohols Ethanol, Methanol, x x x x x Butanol, Alkyl c1-8 Esters FAME,FAEE, x x x x Triglycerides, Vegetable Oils Special Gaseous LPG, CNG,DME, Fuels Hydrogen

indicates data missing or illegible when filed

Fuels and fuel additives and fuel additive packages may also be thecomposition and/or contain the composition of the present invention.Examples can be found in WO01/38461 and/or in GB 2121807 which arehereby incorporated, in their entirety, herein by reference.

The composition of the present invention may be made from a startingcomposition containing greater than 50 ppm sulfur, preferably greaterthan 40 ppm, more preferably greater than 30 ppm, most preferablygreater than 20 ppm and containing the above-mentioned components of theFAC based upon the total weight of the starting composition. Thestarting composition may contain from greater than or equal to 500 to 20ppm of sulfur, preferably from 250 to 20 ppm sulfur, more preferablyfrom 100 to 20 ppm sulfur, based upon the total weight of thecomposition. The starting composition may contain 500, 400, 300, 200,100, 90, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25, and 20 ppm of sulfurbased upon the total weight of the composition, including any and allranges and subranges therein. Examples of the starting material may beany tall oil product such as tall oil fatty acids such as for Examplethose provided by Arizona Chemical Company such as Sylfat SL2, SylfatFA1, Sylfat FA2, Sylfat FA3.

The composition of the present invention may be made by distilling thestarting composition. The distillation step may be conducted using anydistillation means. Examples 20 of such distillation means include ashort-path distillation column, a wiped film evaporator, a continuouscolumn, a continuous fractionation column, or combinations thereof.

In one embodiment, the starting material is continuously distilled atany temperature and pressure conventionally known in the art.

Alternatively, the present invention may be made contacting and/orstirring the above-mentioned starting composition with an adsorbent,preferably stirred and/or contacted in a regeneratable column. While theadsorbent may be any material having adsorbing means, the adsorbent maybe clay, acid-activated clay, silica, activated carbon containingcompound, diatomaceous earth, or combinations and/or mixtures thereof.Preferably the adsorbent is a clay, more preferably an acid-activatedclay.

Examples of a silica include any commercially available silica, such asthose from Ineos, such as for example GASIL U623. Examples of the clayinclude any commercially available clay. Further clays includeacid-activated clays such as for example acid activated bentonite and/ormontmorillonite such as those from Englehard such as F1 and F20 and/orSud-Chemie such as Tonsil Supreme 110 FF.

If a clay is used as an adsorbent, the particle size distribution may beany particle size distribution so long as it is capable of producing thelow sulfur containing composition of the present invention. For example,the particle size may be such that legs than 15%, preferably less than12%, more preferably less than 10% of the particles have a size that isgreater than 150 microns. In a further embodiment, the particle size maybe such that less than 25%, preferably less than 22%, more preferablyless than 20% of the particles have a size that is greater than 100microns. In a further embodiment, the particle size may be such thatless than 35%, preferably less than 32%, more preferably less than 30%of the particles have a size that is greater than 63 microns. In afurther embodiment, the particle size may be such that less than 65%,preferably less than 62%, more preferably less than 60% of the particleshave a size that is greater than 45 microns. In a further embodiment,the particle size may be such that less than 35%, preferably less than32%, more preferably less than 30% of the particles have a size that isgreater than 25 microns. This is especially true when the adsorbent is aclay or acid-modified clay.

While the clay may be of any distribution, including the exemplifiedembodiments mentioned above, a preferred embodiment of a clay to be usedas an adsorbent in the adsorbing step, yet is not intended to belimiting, has a particle size distribution such that, clay about 8% ofthe particles have a size that is greater than 150 microns, about 18%greater than 100 microns, about 28% greater than 63 microns, about 38%greater than 45 microns, and about 58% is greater than 25 microns.

While any amount of adsorbent may be used at the adsorbing step theamount of absorbent used may be greater than 0.001%, preferably greaterthan 0.01%, more preferably greater than 0.1%, most preferably greaterthan or equal to 1% of adsorbent based upon the total weight of thecomposition being subjected to the adsorbing step. Further, the amountof absorbent used may be less than 50, preferably less than 40, morepreferably less than 20, most preferably less than 10 wt % of adsorbentbased upon the total weight of the composition being subjected to theadsorbing step. The amount of the adsorbent may be 0.001, 0.01, 0.1, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 40 and 50% of adsorbentbased upon the total weight of the composition being subjected to theadsorbing step, including any and all ranges and subranges therein.

While the adsorbing step may use any adsorbent, the adsorbent may havean average pore size of from 10 to 250, preferably from 20 to 150, morepreferably from 40 to 100, most preferably from 50 to 75 angstroms. Thepore size of the adsorbent may be 10, 20, 30, 40, 45, 50, 55, 60, 65,70, 75, 80, 90, 100, 125, 150, 175, 200, 225, and 250 angstroms,including any and all ranges and subranges therein. This is especiallytrue when the adsorbent is a silica and mixtures of silicas having poresize of from 60 to 100 angstroms is preferred.

The adsorbing step and the distilling step may be used in isolation orin combination with one another. Preferably the adsorbing step isconducted to produce the composition of the present invention. However,if the distilling step and the adsorbing step are used in combination,preferably they are used serially to produce the composition of thepresent invention. While the distilling step may be conducted before orafter the adsorbing step, it is preferable that the distilling stepoccur prior to the adsorbing step.

In one embodiment, the starting material is continuously distilled priorto the adsorbing. In this embodiment, any “cut”, or portion of thedistilled starting material, and/or combination of cuts from the columnmay be removed and distilled. Typically, there may be three portions tothe distilling apparatus: a top cut, a bottom cut, and a body or heartor middle cut. In an exemplified embodiment, a 75% heart cut may beremoved from the distillation apparatus and subjected to adsorbing.While any % heart cut may be removed and subjected to the adsorbing, itis preferable that at least a 40% heart cut is removed. A material thatis subjected to the adsorbing may be any cut, but preferably may be acut containing from 40 to 95% heart cut, more preferably from 50 to 90%heart cut. The cut may be a 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90,and 95% heart cut.

When a “heart” cut is taken from the distilling apparatus, at least aportion of the top cut and/or at least a portion of the bottom cut isremoved and discarded therefrom (i.e. not subjected to the adsorbing).In an additional embodiment, the portion that is removed may be from 0to 50% of the top cut. Therefore, the cut that is subjected to theadsorbing may be one created by removing 0, 5, 10, 15, 20, 25, 30, 35,40, 45, and 50% of the top cut, including any and all ranges andsubranges therein.

In another embodiment, the portion that is removed may be from 0 to 50%of the bottom cut. Therefore, the cut that is subjected to the adsorbingmay be one created by removing 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, and50% of the bottom cut, including any and all ranges and subrangestherein.

In another embodiment, the heart cut that is subjected to the adsorbingmay be created by removing combinations of the top cut and the bottomcut. Any of the above portions of top cut and bottom cut may becombined, so long as the total % removed of the top and bottom cuts doesnot add up to more than 40%. However, this is due predominantly toeconomics and the present invention may also be achieved by removing thetop and/or bottom cuts so as that they total an amount equal to morethat 40%. In an example not intended to be limiting, a 75% heart cut maybe taken from the distillation apparatus and subjected to the adsorbingby removing therefrom about 5% of the bottom cut and 20% of the top cut.In this embodiment when both a portion of the top cut and a portion ofthe bottom cut are removed, the ratio of the portions of the top andbottom cuts removed from the heart cut prior to subjecting the heart cutto the adsorbing may be from 1:50 to 50:1, preferably 1:25 to 25:1, morepreferably, from 1:15 to 15:1, most preferably from 1:10 to 10:1. Thisrange includes 1:50, 1:40, 1:30, 1:20, 1:10, 1:9; 1:8, 1:7, 1:6, 1:5,1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1,30:1, 40:1, and 50:1, including any and all ranges and subrangestherein.

Most preferably, the components that make up the starting material arevery similar to the components of the FAC of the present inventionexcept that the level of sulfur in the starting composition is greater.These components, their identities and their relative amounts of fattyacids within the starting material are not materially changed and/or areminimally adjusted as the sulfur content is extracted therefrom viacontacting the starting material with the adsorbent above. Mostpreferably, no change occurs at all or less than 5% of that wt % in thestarting material for each component: hydrocarbon, rosin acid, and/orunsaponifiable.

The composition of the present invention, when containing low sulfur,may further be utilized as a starting composition for esterificationand/or hydrogenation so as to obtain fatty alcohols low in sulfur. Suchalcohols may be used in cosmetics, neutraceuticals, fuels,pharmaceuticals, etc. This includes dimers and trimers thereof, as wellas methyl and/or ethyl esters thereof.

The sulfur content may be measured by standard tests, including ASTM D5453 (Antec device) with UV fluorescence and/or ASTM D1822.

The present invention is explained in more detail with the aid of thefollowing embodiment examples.

EXAMPLES

The impact of distillation and adsorbing steps on the sulfur content ofa commercially standard TOFA (i.e. Sylfat 2LT from Arizona ChemicalCompany) was determined by the following experiment.

The TOFA was optionally distilled in a continuous distillation column atabout 190° C. under 2 mm Hg of pressure. When distilled, a 75% heart cutwas then subjected to the below described adsorbing treatment. About 5%of the bottom cut was removed and about 20% of the top cut was removedto create the 75% heart cut was then subjected to the below describedadsorbing treatment.

Varying amounts (i.e. 0, 1, 2, 3, 4, and 5% based upon the total weightof the heart cut) of the adsorbent, i.e. Tonsil Supreme 110 FF fromSud-Chemie as the clay or GASIL IJ623 from Ineos as the silica) wascontacted with the fatty acid (either distilled as mentioned above orundistilled) for 10 minutes, removed by filtration filter to produce theinventive material.

The sulfur content for each of the above was measured using standardtests, in this case ASTM D 5453 (Antec device) with UV fluorescence. Theresultant sulfur content of the distilled or undistilled TOFA afterbeing subjected to different amounts of adsorbent (silica or clay) arereported in FIGS. 1 and 2. FIG. 1 shows the results when distilled orundistilled TOFA is subjected to various amounts (1-5%) silicaadsorbent, while FIG. 2 shows the results when distilled or undistilledTOFA is subjected to various amounts (1-5%) clay adsorbent.

As used throughout, ranges are used as a short hand for describing eachand every value that is within the range, including all subrangestherein.

Numerous modifications and variations on the present invention arepossible in light of the above teachings. It is, therefore, to beunderstood that within the scope of the accompanying claims, theinvention may be practiced otherwise than as specifically describedherein.

All of the references, as well as their cited references, cited hereinare hereby incorporated by reference with respect to relative portionsrelated to the subject matter of the present invention and all of itsembodiments

1-4. (canceled)
 5. A method of making a low sulfur composition,comprising contacting and/or stirring a high sulfur compositioncomprising: from 85 to 99.9% by weight of at least one saturated orunsaturated, monocarboxylic aliphatic hydrocarbon having a linear,branched, and/or cyclic chain of from 8 to 24 carbon atoms, a dimerthereof, a trimer thereof, or mixtures thereof; from 0.1 to 15% byweight of at least one cyclic fatty acid compound selected from thegroup consisting of natural resin-based acids obtained from residues ofdistillation of natural oils, amine carboxylates and ester and nitrilecompounds of these acids; and greater than 25 ppm of sulfur with anadsorbent having an average pore size of from 10 to 250 angstroms toform a low sulfur composition having less than or equal to 25 ppm ofsulfur.
 6. The method according to claim 5, wherein the high sulfurcomposition comprises greater than or equal to 30 ppm of sulfur.
 7. Themethod according to claim 5, wherein the high sulfur compositioncomprises greater than or equal to 40 ppm of sulfur.
 8. The methodaccording to claim 5, wherein the adsorbent comprises at least onemember selected from the group consisting of activated carbon containingcompound, silica, alumina, clay, acid-activated clay, and diatomaceousearth.
 9. The method according to claim 5, wherein the adsorbent has anaverage pore size of from 40 to 100 angstroms.
 10. The method accordingto claim 5, wherein the adsorbent has an average pore size of from 50 to75 angstroms.
 11. The method according to claim 5, wherein the adsorbentis at least one adsorbent selected from the group consisting of silicaand clay.
 12. The method according to claim 5, wherein the adsorbent isat least one acid-activated clay.
 13. The method according to claim 5,further comprising distilling the high sulfur composition prior to thecontacting step.
 14. The method according to claim 13, wherein the highsulfur composition comprises greater than or equal to 40 ppm of sulfurprior to said distilling step.
 15. The method according to claim 13,wherein the high sulfur composition comprises greater than or equal to60 ppm of sulfur prior to said distilling step.
 16. The method accordingto claim 13, wherein the distilling is performed by a short-pathdistillation column.
 17. The method according to claim 16, wherein theshort-path distillation column is a wiped film evaporator.
 18. Themethod according to claim 13, wherein the distilling is performed by acontinuous column, a continuous fractionation distillation column, or acombination thereof. 19-30. (canceled)
 31. A low sulfur compositionprepared according to the method of claim
 5. 32. The low sulfurcomposition of claim 31, comprising less than or equal to 20 ppm ofsulfur.
 33. The low sulfur composition of claim 31, comprising less thanor equal to 15 ppm of sulfur.